Disperse mono- and bisazo dyes derived from 2-amino-4,5-dicyanoimidazole

ABSTRACT

Azo dyes free of water solubilizing groups having the formula ##STR1## WHEREIN R 1  is C 1-4  alkyl, --CH 2  --CH═CH 2 , ##STR2## --(CH 2 ) n  R 8 , C 1-4  alkyleneCN, C 2  H 4  OR 7 , --CH 2  --CH═CH--R 8 , --C 2  H 4  CONH 2 , --C 2  H 4  CONHC 1-4  alkyl, --C 2  H 4  CON(C 1-4  alkyl) 2  and --C 2  H 4  CO 2  C 1-4  alkyl; A is a coupling component selected from: a 5- or 6-membered heterocycle consisting of 5-aminopyrazole, 5-pyrazolone, barbituric acid, 6-hydroxypyrid-2-one, 4-hydroxycoumarin and 1,2-dialkylindole; a 1- or 2-naphthol group and an aromatic amine of the formula ##STR3## W is 1,4-naphthylene or ##STR4## R 2  is H, F, Cl, C 1-4  alkyl, OC 1-4  alkyl; R 3  is cyclohexyl or C 1-14  alkylene-R 9  ; R 2  and R 3  together with the nitrogen atom optionally form a 6-membered ring optionally substituted with --OH, OC 2  H 4  CN or OCOC 1-5  alkyl; R 4  is H, ##STR5## R 3  and R 4  together optionally form a 6-membered heterocyclic ring containing the nitrogen atom; R 5  is H; R 6  is H, F, Cl, Br, C 1-4  alkyl, OC 1-4  alkyl, OH, C 1-4  hydroxyalkyl, NHCOCH═CH 2 , NHCOC 1-4  alkyl, NHCOR 8 , NHCO 2  C 1-4  alkyl, NHCONHC 1-4  alkyl, NHSO 2  C 1-4  alkyl, NHSO 2  R 8 , NHCO 2  R 8 , NHCONHR 8 , NHCOC 1-4  alkylene-R 10 , NHCOC 1-4  alkylene-OC 1-4  alkylene-R 10 , NHCO 2  C 11-4  alkyleneOC 1-4  alkyl; R 5  and R 6  together optionally form --CH═CH--CH═CH--; R 7  is H or C 1-4  acyl; R 8  is phenyl or phenyl optionally substituted with 1-2 groups selected from Cl, Br, CN, CF 3 , NO 2 , C 1-4  alkyl, OC 1-4  alkyl, N(C 1-4  alkyl) 2  and NHCOC 1-4  alkyl; R 9  is H, OH, CN, COC 1-4  alkyl, OCOCH═CH 2 , OCOC 1-4  alkylene-R 11 , OCOR 8 , CO 2  R 8 , CO 2  C 1-4  alkylene-R 12 , ##STR6## OC 1-4  alkylene-R 10 , CONHC 1-4  alkylene-R 11 , SO 2  R 8 , OCONHC 1-4  alkylene-R 10 , NHCOC 1-4  alkylene-R 10 , NHCONHR 8 , NHCOR 8  or R 8  ; R 10  is CN, OH, Cl, Br or R 7  ; R 11  is H, Cl, Br, OC 1-4  alkyl or phenyl; R 12  is H, OH, OC 1-4  alkyl, OCOC 1-4  alkylene-R 11  or OCOR 8  ; R 13  and R 14  are independently H, C 1-4  alkyl, C 1-4  alkyl, C 1-4  alkoxy or Cl; m is 0 or 1; and n is 1 to 3.

BACKGROUND AND OBJECTS OF THE INVENTION

The dye trade is continuously seeking new and better dyes for use inexisting dyeing and printing systems, newly developed systems and withdifferent fibers, which materials may, for example, be subjected to anaftertreatment (after dyeing) step, such as the application of apermanent press resin composition, to impart an additional disirableproperty to the dyed fiber.

In addition, dyes which combine brightness of shade and high tinctorialstrength with good application and fastness properties are particularlyuseful in such systems. Bright dyes are more attractive than dull dyesand offer greater versatility in formulating mixed shades. Commercialdisperse dyes for use on polyester and other synthetic and semisyntheticfibers tend as a class to have rather dull shades. Bright disperse dyesoften suffer from poor lightfastness or high cost, or both.

Heterocylic azo dyes are valued for their brightness and tinctorialstrength. However, few have reached commercial importance, often becauseof poor fastness properties or lack of economical synthetic proceduresfor their manufacture.

It is an object of this invention to provide yellow to blue shadedisperse dyes. It is a further object to provide bright, tinctoriallystrong disperse dyes. It is a still further object to provide dispersedyes with good to excellent fastness to light and sublimation onpolyester and polyester-cellulosic blend fibers. These and other objectsare fulfilled by the following invention.

SUMMARY OF THE INVENTION

The present invention is concerned with azo dyes free of watersolubilizing groups, which have the formula ##STR7## wherein R₁ isselected from the group consisting of C₁₋₄ alkyl, --CH₂ --CH═CH₂,##STR8## --(CH₂)_(n) R₈, C₁₋₄ alkyleneCN, C₂ H₄ OR₇, --CH₂ --CH═CH-R₈,--C₂ H₄ CONH₂, --C₂ H₄ CONHC₁₋₄ alkyl, --C₂ H₄ CON(C₁₋₄ alkyl)₂, and--C₂ H₄ CO₂ C₁₋₄ --alkyl, A is selected from the group consisting of aheterocycle, a naphthol coupler, and an amine of the formula ##STR9## Wis 1,4-naphthylene or ##STR10## R₂ is H, F, Cl, C₁₋₄ alkyl, OC₁₋₄ alkyl;R₃ is cyclohexyl or C₁₋₄ alkylene-R₉ ; or R₂ and R₃ together can form a6-membered ring optionally substituted with --OH, OC₂ H₄ CN or OCOC₁₋₅alkyl; R₄ is H, ##STR11## or R₃ and R₄ together form a heterocyclic ringcontaining the nitrogen atom; R₅ is H; R₆ is H, F, Cl, Br, C₁₋₄ alkyl,OC₁₋₄ alkyl, OH, C₁₋₄ hydroxyalkyl, NHCOCH═CH₂, NHCOC₁₋₄ alkyl, NHCOR₈,NHCO₂ C₁₋₄ alkyl, NHCONHC₁₋₄ alkyl, NHSO₂ C₁₋₄ alkyl, NHSO₂ R₈, NHCO₂R₈, NHCONHR₈, NHCOC₁₋₄ alylene-R₁₀, NHCOC₁₋₄ alkylene-OC₁₋₄alkylene-R₁₀, NHCO₂ C₁₋₄ alkyleneOC₁₋₄ alkyl; or R₅ and R₆ together are-CH═CH-CH═CH-; R₇ is H or C₁₋₄ acyl; R₈ is phenyl or phenyl optionallysubstituted with 1-2 groups selected from Cl, Br, CN, CF₃, NO₂, C₁₋₄alkyl, OC₁₋₄ alkyl, N(C₁₋₄ alkyl)₂ and NHCOC₁₋₄ alkyl; R₉ is H, OH, CN,COC₁₋₄ -alkyl, OCOCH═CH₂, OCOC₁₋₄ alkylene-R₁₁, OCOR₈, CO₂ R₈, CO₂ C₁₋₄alkylene-R₁₂, ##STR12## OC₁₋₄ alylene-R₁₀, CONHC₁₋₄ alkylene-R₁₁, SO₂R₈, OCONHC₁₋₄ alkylene-R₁₀, NHCOC₁₋₄ -alkylene-R₁₀, NHCONHR₈, NHCOR₈ orR_(8;) R₁₀ is CN, OH, Cl, Br or R₇ ; R₁₁ is H, Cl, Br, OC₁₋₄ alyl orphenyl; R₁₂ is H, OH, OC₁₋₄ alkyl, OCOC₁₋₄ alkylene-R₁₁ or OCOR₈ ; R₁₃and R₁₄ are independently H, C₁₋₄ alkyl, C₁₋₄ alkoxy or Cl; m is 0 or 1and n is 1 to 3.

The present invention also relates to the process for preparing theheretofore defined mono- and bisazo dyes, said process consisting offirst diazotizing 2-amino-4,5-dicyanoimidazole by conventional means andsubsequently coupling to compounds defined by A above to provide theintermediate monoazo compounds of the following generic structure:##STR13##

Coupling of 2-diazo-4,5-dicyanoimidazole to α-naphthylamine or an amineof the formula ##STR14## where R₁₃ and R₁₄ are as previously definedabove, provides an intermediate monoazo amine which is subsequentlydiazotized and coupled to compounds defined by A above to yield theintermediate bisazo compounds of the following generic structure##STR15## where W and A are as previously defined.

In a subsequent step, the above intermediate mono- and bisazo compoundsare alkylated on one of the imidazole nitrogens as hereinafter describedto introduce the R₁ radical, thus providing the dyes of the presentinvention having the following generic structure ##STR16## where R₁, W,A and m are as previously defined.

The preparation of 2-amino-4,5-dicyanimidazole was carried outessentially as described by Webster in coassigned patent applicationSer. No. 146,754 by treatment of diaminomaleonitrile with a 10% molarexcess of cyanogen chloride in tetrahydrofuran solvent at 25°-30° C.

The diazotization of 2-amino-4,5-dicyanoimidazole can be carried out atfrom 8° to 25° C., with a range of 20°-25° C. being most convenient, bythe action of sodium nitrite in aqueous mineral acid, e.g. HCl. The2-diazo-4,5-dicyanoimidazole precipitates quantitatively and can befiltered off and dried under an air stream or in a vacuum. However, dry2-diazo-4,5-dicyanoimidazole is highly shock sensitive and detonates at150° C. In order to avoid explosions, the water-wet suspension of thediazonium zwitterion is preferably used directly in the subsequentcoupling step.

Coupling to aromatic amines to provide the intermediate monoazocompounds of this invention is carried out by dissolving the aminecoupler (defined by A) in a suitable solvent, which in some cases can beaqueous mineral acid and/or aqueous acetic acid but more usually is asolvent such as methanol, ethanol or a mixture of one of these andacetic acid, and then slowly adding the coupler solution to thediazonium zwitterion slurry, or vice versa. Equimolar proportions or upto a 10% molar excess of coupler to 2-amino-4,5-dicyanoimidazole areoperable. A 10% molar excess of coupler is particularly perferred.Coupling temperatures in the range from 8° to 25° C. are operable and20°-25° C. is preferred for convenience. Time for the coupling reactionmay vary from a few minutes (e.g. 5) up to 24 hours, depending somewhaton the temperature and the reactivity of the coupler employed. Aqueoussodium acetate may be added at this point, in some cases, to neutralizethe strong mineral acid and raise the pH to 3.0-4.0 in order to obtaincomplete coupling. Addition of sodium acetate can also help to coagulatethe dye and provide a better filtering crystal form even when couplingis complete at low mineral acid pH. The dye product is insoluble andreadily precipitates even prior to the sodium acetate addition. The dyeis then isolated by filtration, washed with water and dried.

The intermediate bisazo compounds of this invention are prepared bycoupling 2-diazo-4,5-dicyanoimidazole to 2-naphthylamine or an amine ofthe formula ##STR17## where R₁₃ and R₁₄ are as previously defined. TableI lists examples of such amines.

TABLE I

aniline

o- or m-toluidine

o- or m-ethylaniline

o- or m-anisidine

o- or m-phenetidine

o- or m-chloroaniline

2,5-xylidine

2,5-dimethoxyaniline

2,5-diethoxyaniline

5-chloro-o-toluidine

5-chloro-o-anisidine

5-methyl-o-anisidine

Coupling is preferably effected at 20°-25° C. by dissolving the aminetotally or partially in dilute mineral acid and/or an organic solventsuch as acetic acid and/or methanol and then slowly adding the diazoniumzwitterion preparation, or vice versa. When the coupling is complete,the reaction mixture is advantageously neutralized with caustic and themonoazo product is isolated by filtration.

The monoazo amine thus obtained is conveniently diazotized in aqueousacetic acid by adding hydrochloric acid and sodium nitrite at 10°-25°C., preferably at 20°-25° C., and coupled to the final couplingcomponent as defined by A by an identical procedure to that describedabove.

Substituted aniline couplers useful in the practice of this inventionare given in Table II.

                                      Table II                                    __________________________________________________________________________    Substituted Aniline Couplers Useful in the Practice of this Invention          ##STR18##                                                                    R.sub.2                                                                           R.sub.3              R.sub.4         R.sub.5                                                                         R.sub.6                            __________________________________________________________________________    H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 OC.sub.6 H.sub.5                                                      H CH.sub.3                           H   CH.sub.3             CH.sub.3        H NHCOC.sub.6 H.sub.5                H   C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                                  C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   CH.sub.2 C.sub.6 H.sub.5                                                                           CH.sub.2 C.sub.6 H.sub.5                                                                      H NHCOCH.sub.3                       H   (CH.sub.2).sub.3 CH.sub.3                                                                          (CH.sub.2).sub.3 CH.sub.3                                                                     H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      CH.sub.2 C.sub.6 H.sub. 5                                                                     H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 CH.sub.3                                                              H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H CH.sub.3                           H   C.sub.2 H.sub.5      C.sub.2 H.sub.4 OH                                                                            H CH.sub.3                           OCH.sub.3                                                                         C.sub.2 H.sub.4 CN   H               H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.4 CN                                                                            H CH.sub.3                           CH.sub.2 CH(OC.sub.2 H.sub.4 CN)CH.sub.2                                                               C.sub.2 H.sub.5 H CH.sub.3                           H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OH                                                                            H CH.sub.3                           H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H CH.sub.3                           H   CH(CH.sub.3).sub.2   CH.sub.2 CH(OCOCH.sub.3)C.sub.2 H.sub.5                                                       H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)C.sub.2 H.sub.5                                                       H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OH                                                                            H NHCOCH.sub.3                       H   C.sub. 2 H.sub.4 CN  CH.sub.2 CH(OH)C.sub.2 H.sub.5                                                                H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H H                                  H   (CH.sub.2).sub.3 CH.sub.3                                                                          (CH.sub.2).sub.3 CH.sub.3                                                                     H H                                  H   CH(CH.sub.3)CH.sub.2 CN                                                                            H               H H                                  H   C.sub.2 H.sub.4 CN   CH.sub.2 CH.sub.2 CH.sub.3                                                                    H H                                  H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 OH   C.sub.2 H.sub.4 OH                                                                            H H                                  H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OCOC.sub.6 H.sub.5                                                            H H                                  H   C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7                                                                 C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7                                                            H H                                  H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                               H H                                  H   C.sub.2 H.sub.4 OCO(CH.sub.2).sub.3 CH.sub.3                                                       C.sub.2 H.sub.4 OCO(CH.sub.2).sub.3 CH.sub.3                                                  H H                                  H   C.sub.2 H.sub.4 OCOCHCH.sub.2                                                                      C.sub.2 H.sub.4 CN                                                                            H Cl                                 H   C.sub.2 H.sub.4 CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                 H               H Cl                                 H   C.sub.2 H.sub.4 CN   C.sub. 2 H.sub.4 CN                                                                           H Br                                 H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OH                                                                            H C.sub.4 H.sub.9                    H   CH.sub.3             CH.sub.3        H NHCOC(CH.sub.3).sub.3              H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHSO.sub.2 CH.sub.3                H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCONHC.sub.2 H.sub.5              H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 CH.sub.3                H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOC.sub.3 H.sub.7                H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCONHC.sub.4 H.sub.9              H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.4 H.sub.9         H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.2 H.sub.4                                                    OC.sub.2 H.sub.5                   H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.2 H.sub.5         H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOCH.sub.2 OC.sub.2 H.sub.5      H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOCH.sub.2 Cl                    H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHSO.sub.2 CH.sub. 3               H   C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                                 C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                            H NHCOC.sub.2 H.sub.5                H   C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7                                                                 C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7                                                            H NHCOC.sub.3 H.sub.7                H   C.sub.2 H.sub.5      CH.sub.2 C.sub.6 H.sub.5                                                                      H CH.sub.3                           H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)C.sub.2 H.sub.5                                                                H CH.sub.3                           H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H CH(OH)CH.sub.3                     H   C.sub.2 H.sub.5      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H CH.sub.3                           H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H OH                                 H   C.sub.2 H.sub.4 OH   C.sub.2 H.sub.4 OH                                                                            H CH.sub.3                           H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                          H               H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.6 H.sub.4 -(3')N(CH.sub.3).sub.2                                    H               H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.6 H.sub.4 -(3')CF.sub.3                                             C.sub.2 H.sub.5 H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.6 H.sub.3 -(3',5')(Cl.sub.2)                                        C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.6 H.sub.4 -(4')OCH.sub.3                                            C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.6 H.sub.3 -(4')OCH.sub.3,(2')CH.sub.3                               C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   CH.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.6 H.sub.4 -(4')C(CH.sub.3).sub.3                               H               H CH.sub.3                           H   C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4 -(2')Cl                                                         C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4 -(4')NO.sub.2                                                   C.sub.2 H.sub.5 H CH.sub.3                           H   C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4 -(4')NHCOCH.sub.3                                               C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 OCOC.sub.6 H.sub.3 -(2')Cl, (4')NO.sub.2                                           C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.5                H   C.sub.2 H.sub.4 OCOCH.sub.2 CH(C.sub.6 H.sub.5)CH.sub.3                                            C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.6 H.sub.3 -(2')CH.su        b.3, (3')NO.sub.2    C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   CH.sub.2 CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.4 -(4')Br                                              C.sub.2 H.sub.5 H H                                  H   CH.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4              -(4')OCH.sub.3       C.sub.2 H.sub.5 H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4 -(3')CN                                C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.6 H.sub.4 -(2')CH.su        b.3                  H               H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 C.sub.6           H.sub.5              H               H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOCH.sub.2 Cl                                            C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.5                H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.3 H.sub.7                                          H               H Cl                                 H   CH(CH.sub.3)CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                  H               H CH.sub.3                           H   C.sub.2 H.sub.4 CO.sub.2 CH.sub.2 CH(OCH.sub.3)CH.sub.3                                            C.sub.2 H.sub.5 H Br                                 H   C.sub.2 H.sub.4 CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH                                             C.sub.2 H.sub.5 H CH.sub.3                                ##STR19##           C.sub.2 H.sub.5 H H                                  F   C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                                 C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7                                        C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                      OCOC.sub.3 H.sub.7                                                                            H H                                  C.sub.4 H.sub.9                                                                   C.sub.2 H.sub.5      C.sub.2 H.sub.4 CN                                                                            H Cl                                 Cl  C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 OCH.sub.3                                                       C.sub.2 H.sub.4 CN                                                                            H H                                  OC.sub.4 H.sub.9                                                                  C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H H                                  H   C.sub.2 H.sub.5      CH.sub.2 CH.sub.2 CH.sub.2 CN                                                                 H F                                  H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.4 OCH.sub.3      H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H NHCO(CH.sub.3).sub.3 CH.sub.3      H   CH.sub.2 CH.sub.2 CH.sub.3                                                                         C.sub.2 H.sub.4 C.sub. 6 H.sub.5                                                              H NHCOC.sub.2 H.sub.4 Cl             OCH.sub.3                                                                         C.sub.2 H.sub.5      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H NHCOCH.sub.3                       OC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OH                                                        H               H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOC.sub.6 H.sub.4 -(3')CH.sub                                               .3                                 OCH.sub.3                                                                         C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOCH.sub.2 Cl                    OCH.sub.3                                                                         C.sub.2 H.sub.4 OH   C.sub.2 H.sub.4 OH                                                                            H NHCOCH.sub.2 CH(Cl)CH.sub.3        OCH.sub.3                                                                         C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCOCH.sub.3                                               C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                      OCOCH.sub.3     H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHCOC.sub.6 H.sub.4 -(2')Cl        OCH.sub.3                                                                         C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHCO(CH.sub.2).sub.3 CH.sub.2                                                 Br                                 OCH.sub.3                                                                         C.sub.2 H.sub.4 OH   C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                             H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.4 OH   C.sub.2 H.sub.4 CN                                                                            H NHCOC.sub.6 H.sub.4                                                           -(4')NO.sub.2                      CH.sub.2 CH(OH)CH.sub.2  H               CHCHCHCH                             CH.sub.2 CH(OCOC.sub.5 H.sub.11)CH.sub.2                                                               H               CHCHCHCH                             H                                                                                 ##STR20##            H               CHCHCHCH                             H  C.sub.2 H.sub.5       H               CHCHCHCH                             H  C.sub.2 H.sub.5       C.sub.2 H.sub.5 CHCHCHCH                             OCH.sub.3                                                                        C.sub.2 H.sub.5       C.sub.2 H.sub.5 CHCHCHCH                             H  C.sub.2 H.sub.4 CONHCH.sub.3                                                                        H               CHCHCHCH                             H  C.sub.2 H.sub.4 CN    H               CHCHCHCH                             H   C.sub.2 H.sub.4 C    CH.sub.2 CH(OH)CH.sub.2 Cl                                                                    H CH.sub.3                           H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 Cl                                                           H H                                  H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOC.sub.4 H.sub.9)CH.sub.2 Br                                                    H Cl                                 H   C.sub.2 H.sub. 4 CN  CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 Cl                                                           H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OH)CH.sub.2 Cl                                                                    H NHCOCH.sub.3                       OCH.sub.3                                                                         C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 Cl                                                           H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OC.sub.6                                     H.sub.5         H Cl                                 H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OC.sub.6                                                     H.sub.4                                                                         CH.sub.3                                                     . (4')CH.sub.3                                      H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OC.sub.6                                                     H.sub.4                                                                         CH.sub.3                                                    (4')OCH.sub.3                                        H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOC.sub.2 H.sub.5)CH.sub.2 OC.sub.6                              H.sub.5         H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOC.sub.2 H.sub.5)CH.sub.2 OC.sub.2                              H.sub.5         H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN   CH.sub.2 CH(OCOCH.sub.3)CH.sub.2 OC.sub.4                                     H.sub.9         4 NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H OCH.sub.3                          H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H OC.sub.2 H.sub.5                   H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.5 H NHCOCHCH.sub.2                     H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHCOC.sub.6 H.sub.5                H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHSO.sub.2 C.sub.2 H.sub.5         H   C.sub.2 H.sub.4 OCOCH.sub.3                                                                        C.sub.2 H.sub.4 OCOCH.sub.3                                                                   H NHSO.sub.2 C.sub.6 H.sub.5         H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.5 H NHSO.sub.2 C.sub.6 H.sub.4                                                    -(4')CH.sub.3                      H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.6 H.sub.4                                                    -(4')CH.sub.3                      H   C.sub.2 H.sub.4 CN   C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.6 H.sub.4                                                    -(4')Br                            H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCONHC.sub.6 H.sub.5              H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCONHC.sub.6 H.sub.4 -(4')Cl      H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.2 H.sub.4                                                    OC.sub.4 H.sub.9                   H   C.sub.2 H.sub.4 COC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 COC.sub.2 H.sub.5                                                             H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 Br                                                              C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 OCOCH.sub.2 CH.sub.2 CH.sub.2 Cl                                                   C.sub.2 H.sub.4 CN                                                                            H H                                  H   C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                C.sub.2 H.sub.4 OCOC.sub.2 H.sub.4 OC.sub.2                                   H.sub.5         H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3                                                 C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                      OCH.sub.3       H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OH                                                        C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                                      HH                                                                              NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CONHC.sub.2 H.sub.4 Cl                                                             C.sub.2 H.sub.5 H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CONHCH.sub.2 CH.sub.2 CH.sub.2 Cl                                                  C.sub.2 H.sub.4 CONHCH.sub.2 CH.sub.2 CH.sub.2                                Cl              H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 SO.sub.2 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.5 H H                                  H   C.sub.2 H.sub.4 SO.sub.2 C.sub.6 H.sub.4 -(4')CH.sub.3                                             H               H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 SO.sub.2 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 SO.sub.2 C.sub.6 H.sub.5                                                      H NHCOCH.sub. 3                      H   C.sub.2 H.sub.5                                                                                     ##STR21##      H NHCOCH.sub.3                       H   C.sub.2 H.sub.4 CN                                                                                  ##STR22##      H CH.sub.3                           H   C.sub.2 H.sub.4 CONHC.sub.2 H.sub.4 OCH.sub.3                                                      C.sub.2 H.sub.4 CONHC.sub.2 H.sub.4 OCH.sub.3                                                 H NHCOCH.sub.3                       H                                                                                  ##STR23##           H               H CH.sub.3                           H                                                                                  ##STR24##           H               H                                                                                ##STR25##                         OCH.sub.3                                                                          ##STR26##           H               H                                                                                ##STR27##                         H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)C.sub.6 H.sub.5                                                                H H                                  H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 Cl                                                                    H CH.sub.3                           H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H Cl                                 H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.5                H   CH.sub.3             CH.sub.3        H NHCOCH.sub.3                       H   C.sub.2 H.sub.5      C.sub.2 H.sub.5 H NHCOC(CH.sub.3).sub.3              H   C.sub.2 H.sub.5      CH.sub.2 CH(OH)CH.sub.2 CN                                                                    H CH.sub.3                           H   C.sub.2 H.sub.5      CH.sub.2 C.sub.6 H.sub.4 -(3')NO.sub.2                                                        H CH.sub.3                           H   C.sub.2 H.sub.5      CH.sub.2 C.sub.6 H.sub.4 -(4')Cl                                                              H CH.sub.3                           __________________________________________________________________________

Many of the aforementioned aniline couplers can be obtained by methodswell-known in the art, e.g. in British Pat. Nos. 1,297,057, 1,244,978,1,290,901, U.S. Pat. No. 3,639,385 and 3,639,384.

Coupling of 2-diazo-4,5-dicyanoimidazole to naphthol couplers isconveniently carried out by adding a suspension of the diazo compound inan aqueous acidic medium to a solution of the coupling component inwater and/or a water-soluble organic liquid containing an alkali metalhydroxide or carbonate, if necessary, adjusting the pH of the mixture toeffect coupling and thereafter isolating the dyestuff by filtration.Suitable organic liquids include ethanol, 2-ethoxyethanol,dimethylsulfoxide, and the lie. Time for the coupling reaction may varyfrom a few minutes (e.g. 5) up to 24 hours, depending on thetemperature, pH and the reactivity of the coupler employed. Couplingtemperatures in the range from 0° to 25° C. are operable and 20°-25° C.is preferred for convenience. Coupling facilely occurs at pH valuesabove 7 and especially at 9-12.

If a represents a naphthol radical, it can be unsubstituted as well assubstituted by halogens such as chlorine or bromine; sulfonic acid amidegroups substituted at the nitrogen by lower alkyl groups; loweralkylsulfonyl or arylsulfonyl groups; lower alkylcarbonylamino groups;lower alkoxycarbonyl groups and lower alkylcarbamoyl groups where loweralkyl and alkoxy denote from 1 to 4 carbons.

Examples of naphthol couplers useful in the practice of this inventionare given in Table III.

TABLE III Naphthol Couplers Useful in the Practice of this Invention

6-bromo-2-naphthol

4-chloro-1-naphthol

2-chloro-1-naphthol

1-naphthol

2-naphthol

1-acetylamino-7-naphthol

3-methoxycarbonyl-2-naphthol

3-ethoxycarbonyl-2-naphthol

6- N,N-bis(ethyl)sulfamoyl!-2-naphthol

6- N-(sec.-butyl)sulfamoyl!-2-naphthol

6-phenylsulfonyl-2-naphthol

7-phenylsulfonyl-2-naphthol

7-ethylsulfonyl-2-naphthol

6- N,N-bis(n-butyl)sulfamoyl!-2-naphthol

6-n-butylsulfonyl-2-naphthol

3-t-butylcarbamoyl-2-naphthol

3-ethylcarbamoyl-2-naphthol

If A is a heterocycle radical, then it is mainly the radical of a 5- or6-membered heterocycle, particularly one containing nitrogen or oxygen.Preferably A is a radical of the aminopyrazole, pyrazolone, barbituricacid, pyridone, indole or hydroxy coumarin series.

More specifically, A can be a 5-aminopyrazole additionally containing inthe 1-position a phenyl or benzyl group, optionally substituted by loweralkyl, lower aloxy, lower alkylsulfonyl, Cl, Br, CN, loweralkylcarbonylamino, lower alkylsulfonamido or sulfonic acid aryl estergroups.

In addition, A can be a 5-pyrazolone containing in the 1-position alower alkyl or aralkyl group optionally substituted by CN or OH; or aphenyl group, optionally substituted by Cl, NO₂, lower alkyl, loweralkoxy, lower alkylcarbonylamino, lower alkylsulfonyl or loweralkylsulfonamido.

The radical A can also be a barbituric acid optionally substituted ineither the 1- and/or 3-positions by lower alkyl groups which may befurther substituted by hydroxy, lower aloxy, lower alylcarbonyloxy, CNand halogens such as chlorine or bromine; cycloalkyl groups such ascyclohexyl; aralkyl groups such as benzyl and β-phenylethyl; or phenylgroups optionally substituted by Cl, Br, CN, NO₂, CF₃, loweralkylcarbonyl, lower alkylsulfonyl or arylsulfonyl, loweralkylcarbonyloxy, lower alkyl sulfonamido or lower alkylcarbonylamino.

The radical A can also be a 3-cyano-4-methyl-6-hydroxy-pyrid-2-onesubstituted in the 1-position by a lower alkyl group which can beoptionally substituted by hydroxy, lower alkoxy, lower alkylcarbonyloxy;or lower aralkyl such as benzyl or β-phenylethyl; or by phenyl or phenylsubstituted by lower alkyl, lower alkoxy or Cl.

Finally, the radical A can also denote a 4-hydroxy coumarin radicalwhich may be optionally substituted in the 6-position by lower alkyl;lower alkoxy; or halogen; or disubstituted in the 5,6- or 6,7-positionsby lower alkyl.

The term "lower" used in the above discussion in connection with alkyland alkoxy means that these radicals contain from 1 to 6 carbon atoms.

Coupling of diazotized 2-amino-4,5-dicyanoimidazole with heterocycliccoupling components is carried out preferably in an aqueous or aqueousorganic medium under weakly acid, neutral or weakly alkaline conditions,for exmple, in the pH range of 3.5 (acetate buffer) to 9.5(carbonate/bicarbonate buffer) and at temperatures of 0° to about 30° C.with a range of 0°-10° C. being preferred.

Examples of heterocyclic couplers that can be used in the practice ofthis invention are given in Table IV. The heterocyclic couplers can beobtained by methods well-nown in the art, e.g., 5-aminopyrazoles in U.S.Pat. Nos. 3,471,468, 3,356,673 and 3,639,387; 5-pyrazolones in U.S. Pat.Nos. 3,395,138 and 3,206,453; 1,3-disubstituted barbituric acids in U.S.Pat. Nos. 3,341,512 and 3,377,129;3-cyano-4-methyl-6-hydroxy-pyrid-2ones in U.S. Pat. No. 3,640,674; and4-hydroxy coumarins in U.S. Pat. No. 3,344,132.

The intermediate mono- and bisazo compounds prepared as previouslydescribed above are subsequently reacted with suitable alkylating agentsto introduce the R₁ radical and thus provide the novel dyestuffs of thepresent invention.

TABLE IV Heterocyclic Couplers Useful in the Practice of This Invention

1-phenyl-3-methyl-5-aminopyrazole

1-(2'-,3'- or 4'-methylphenyl)-3-methyl-5-aminopyrazole

1-(2'-,3'- or 4'-methoxyphenyl)-3-methyl-5-aminopyrazole

1-(2' or 4'-chlorophenyl)-3-methyl-5aminopyrazole

1-(2'-,4'-dichlorophenyl)-3-methyl-5-aminopyrazole

1-(3'- or 4'-acetylaminophenyl)-3-methyl-5-aminopyrazole

1-benzyl-3-methyl-5-aminopyrazole

1-(3'- or 4'-methylsulfonamidophenyl)-3-methyl-5-aminopyrazole

1-phenyl-3-ethoxy-5-aminopyrazole

1-(4'-methoxyphenyl)-3-methoxy-5-aminopyrazole

1-phenyl-3-methoxycarbonyl-5aminopyrazole

1-phenyl-3-methoxy-5-aminopyrazole

1-(4'-chlorophenyl)-3-methoxy-5aminopyrazole

1-(4'-chlorophenyl)-3-ethoxycarbonyl-5-aminopyrazole

1-(4'-bromophenyl)-3-methoxy-5-aminopyrazole

1(4'-methylsulfonylphenyl)-3-methoxy-5-aminopyrazole

1-(4'-ethylsulfonylphenyl)-3-methoxy-5-aminopyrazole

1-(2'-chlorophenyl)-3-methoxy-5-aminopyrazole

1-(4'-methylphenyl)-3-methoxy-5-aminopyrazole

1-(2'-methoxybenzyl)-5-aminopyrazole

1-(2',3'-dimethoxybenzyl)-5-aminopyrazole

1-(2'-chlorobenzyl)-5-aminopyrazole

1-(2',4'-dichlorobenzyl)-5-aminopyrazole

1-(2',6'-dichlorobenzyl)-5-aminopyrazole

1-(4'-methylbenzyl)-5-aminopyrazole

1-(4'-cyanobenzyl)-5-aminopyrazole

1-(4'-ethylsulfonylbenzyl)-5-aminopyrazole

1-phenyl-3-methyl-5-aminopyrazole-3'-sulfonic acid, phenyl ester

1-phenyl-3-methyl-5aminopyrazole-4'-sulfonic acid, phenyl ester

1-phenyl-3-methyl-5-aminopyrazole-3'-sulfonicacid-(4"-methylphenyl)ester

1-phenyl-3-methyl-5-aminopyrazole-4'-sulfonic acid-(4"chlorophenyl)ester

1-(2'-chlorophenyl)-3-methyl-5-aminopyrazole-5'-sulfonicacid(3"-methoxyphenyl)ester

1-(2'-chlorophenyl)-3-methyl-5-aminopyrazole-5'-sulfonicacid(2"-methylphenyl)ester

1-(2'-chlorophenyl)-3-methyl-5-aminopyrazole-5'-sulfonicacid(4"-chlorophenyl)ester

1-phenyl-3-methyl-5-pyrazolone

1-(β-cyanoethyl)-3-methyl-5-pyrazolone

1-(3'-nitrophenyl)-3-methyl-5-pyrazolone

1-(β -hydroxypropyl)-3-methyl-5-pyrazolone

1-(2'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone

1-(2'-,3'- or 4'-methoxyphenyl)-3-methyl-5-pyrazolone

1-(β -hydroxyphenylethyl)-3-methyl-5-pyrazolone

1-(2'-,3'- or 4'-methylphenyl)-3-methyl-5-pyrazolone

1-(3'- or 4'-acetylaminophenyl)-3-methyl-5-pyrazolone

1-(4'-ethylcarbonylaminophenyl)-3-methyl-5-pyrazolone

1-(4'-t-butylcarbonylaminophenyl)-3-methyl-5-pyrazolone

1-(2'-ethylsulfonylamino-4'-chlorophenyl)-3-methyl-5-pyrazolone

1-(4'-methylsulfonylaminophenyl)-3-methyl-5pyrazolone

1-(3'- or 4'-methylsulfonamidophenyl)-3-methyl-5-pyrazolone

1,3-dimethyl barbituric acid

1,3-dicyclohexyl barbituric acid

1,3-diphenyl barbituric acid

1-phenyl barbituric acid

1-phenyl-3-methyl barbituric acid

1-n-butyl barbituric acid

1,3-di-n-butyl barbituric acid

1-phenyl-3-γ -methoxypropyl barbituric acid

1-phenyl-3-benzyl barbituric acid

1-phenyl-3-β -chloroethyl barbituric acid

1-phenyl-3-β -cyanoethyl barbituric acid

1-phenyl-3-β -hydroxyethyl barbituric acid

1-(3'-chlorophenyl)-3-ethyl barbituric acid

1-(2'-methylphenyl)-3-ethyl barbituric acid

1-(4'-chlorophenyl)-3-methyl barbituric acid

1-(2'-methoxyphenyl)-3-ethyl barbituric acid

1-phenyl-3-cyclohexyl barbituric acid

1-phenyl-3-β -phenylethyl barbituric acid

1-(3',4'-dichlorophenyl)-3-methyl barbituric acid

1-(4'-bromophenyl)-3-γ -methoxypropyl barbituric acid

1-(3'-nitrophenyl)-3-methyl barbituric acid

1-(2'-methyl-5'-chlorophenyl)-3-methyl barbituric acid

1-(4'-methylphenyl)-3-isopropyl barbituric acid

1-(2'-ethoxyphenyl)-3-propyl barbituric acid

1-phenyl-3-n-butyl barbituric acid

1-phenyl-3-isopropyl barbituric acid

1-phenyl-3-β -acetoxyethyl barbituric acid

1-(2'-trifluoromethylphenyl)-3-ethyl barbituric acid

1-(3'-cyanophenyl)-3-ethyl barbituric acid

1-(4'-ethylcarbonylphenyl)-3-isopropyl barbituric acid

1-(4-ethylsulfonylphenyl)-3-ethyl barbituric acid

1-(4'-phenylsulfonylphenyl)-3-methyl barbituric acid

1-(4'-ethylcarbonyloxyphenyl)-3-n-propyl barbituric acid

1-(3'-methylsulfonamidophenyl)-3-ethyl barbituric acid

1-(4'-acetylaminophenyl)-3-n-butyl barbituric acid

1-benzyl-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(2'-tolyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(2'-methoxyphenyl)-3-cyano-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(2',4'-dimethylphenyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(4'-chlorophenyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-phenyl-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(γ -methoxypropyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(β -hydroxyethyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-n-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(β -acetoxyethyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(β-phenylethyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

1-(γ -ethoxypropyl)-3-cyano-4-methyl-6-hydroxypyrid-2-one

4-hydroxy coumarin

4-hydroxy-6-methyl coumarin

4-hydroxy-6,7-dimethyl coumarin

4-hydroxy-5,6-dimethyl coumarin

4-hydroxy-6-methoxy coumarin

4-hydroxy-6-bromo coumarin

4-hydroxy-5,6-diethyl coumarin

2-methylindole

1,2-dimethylindole

Suitable alkylating agents are the esters of strong mineral acids andorganic sulfonic acids of, preferably, lower alcohols containing from 1to 4 carbons. These are chiefly alkyl chlorides, alkyl bromides, aralkylhalides and dialkyl sulfates. The intermediate azo compounds can also beconveniently alkylated by treatment with alkylene oxides, e.g., ethyleneoxide, 1,2-propylene oxide or 1,2-butylene oxide, to yield thecorresponding β -hydroxyalkyl derivatives which can, if desired, befurther acylated. A cyanoethyl substituent can also be advantageouslyintroduced by treatment of the intermediate azo compounds withacylonitrile.

The alkylation can be carried out in either an inert organic oraqueous-organic system in the presence of a suitable acid-binding agent.Suitable organic reaction media include acetone, methyl ethyl ketone,dimethylformamide, dimethylacetamide, tetrahydrofuran, ethylene glycoldimethyl ether, dioxane, acetic acid and the like. Acid-binding agents,such as magnesium oxide, sodium carbonate, potassium carbonate, dibasicsodium phosphate and sodium bicarbonate are operative in the alkylationwith potassium carbonate being the preferred agent. Aqueous organicsolvent mixtures such as acetone-water in conjunction with potassiumcarbonate are especially useful in the process as they provide a mediumfor both solution of the water-soluble acid-being agent and for removalof any residual unalkylated dye which is soluble in aqueous potassiumcarbonate. Solvent mixtures of equal weights of both organic solvent(e.g., acetone) and water are especially preferred. The molecularproportions of intermediate azo compound and alkylating agent employedmay be varied within wide limits, e.g., from 1:2 to 1:5, depending onthe reactivity of the alkylating agent used and the temperature. A molarratio of 1:2 is normally satisfactory, however.

Time for the alkylation may vary from 2 hours up to 5 days againdepending on the reactivity of the alkylating agent employed and thetemperature. The alkylation can be carried out from 25° to 80° C., butpreferably at 25°-30° C. Under more energetic conditions, e.g., 6α-80°C., the second imidazole nitrogen, in some cases, is partially alkylatedand a quaternized cationic dye is also formed. The alkylated dispersedyestuff usually precipitates as it is formed and is collected byfiltration and washed with water to remove inorganic salts. In caseswhere the alkylated dye is soluble in the reaction solvent, e.g.dimethylformamide, the reaction mixture may alternatively be drowned inwater and the precipitated dyestuff subsequently isolated by filtration.

The crude dyestuffs are conveniently converted into a commerciallyuseable form by mixing the crude dye (e.g. ten parts on a 100% basis)with about 2.5 parts of a lignin sulfonate dispersant and water in acolloid or sand mill. Milling is continued until a fine, stable, aqueousdispersion or paste is obtained with dye particle size reduced toapproximately one micron.

The invention dyestuffs have excellent affinity and buildup propertieson synthetic textile materials such as nylon and, in particular, onpolyester textile materials, or blends thereof, thus enabling heavydepths of shade of be obtained. The resulting colorations, which rangein shade from yellow to blue, have good fastness to light, to wettreatments and in particular to dry heat treatments such as thosecarried out at high temperature during pleating operations.

The novel invention dyes can be applied to polyester fibers by anaqueous procedure, preferably under pressure, or by padding polyesterfibers, either singly or in cellulosic blends, with an aqueousdispersion of said dyes followed by dry heat (e.g. Thermosol) fixation.Both dyeing procedures are widely used in the trade. This invention isalso directed to the process of dyeing and printing polyester fibers andtheir cellulosic blends, with the invention dyes, preferably on a fabricwhich is subsequently to receive a durable press treatment. The presentinvention also encompasses polyester fibers and blends of polyesterfibers dyed or printed with an invention dye.

The following examples are given to illustrate the invention. All partsare given by weight.

EXAMPLE 1

2-Amino-4,5-dicyanoimidazole (6.65 parts, 0.050 mole) was suspended in165 parts of water and 15.9 parts of concentrated hydrochloric acid(0.135 mole) at 0°-5° C. 5N Sodium nitrite solution (10.66 parts, 0.052mole) was added dropwise at 0°-5° C., and a positive nitrite test wasmaintained for 30 minutes. Excess nitrite was destroyed with sulfamicacid. This suspension of diazonium zwitterion was used directly in thecoupling step.

A solution of 14.8 parts (0.055 mole) of3-(N-benzyl-N-ethylamino)acetanilide in 40 parts of methanol and 40parts of acetic acid was added dropwise over 15 minutes at 0°-5° C. tothe diazonium zwitterion suspension. The reaction was allowed to warm toroom temperature over 4 hours, the solids collected by filtration,washed acidfree with water and dried to give 20.5 parts (99% yield) ofproduct.

The above dry product (8.24 parts, 0.02 mole) was suspended in 125 partsof acetone. A solution of 7.52 parts (0.055 mole) of potassium carbonatein 125 parts of water was added and the reaction stirred for 5 minutesuntil solution was complete. Diethyl sulfate (15.4 parts, 0.10 mole) wasadded and the reaction mixture stirred at 25°-30° C. for 6 hours. Thesolids were isolated by filtration, washed with water and dried to give7.9 parts (90.0% yield) of red product. Recrystallization fromisopropanol provided an analytically pure sample, a_(max). 141 litersg.⁻¹ cm.⁻¹ at λ_(max). 527 mμ.

The structure of the dye is ##STR28##

EXAMPLE 2

To a stirred suspension of 6.65 parts (0.050 mole) of2-amino-4,5-dicyanoimidazole in 160 parts of water and 7.91 parts (0.081mole) of concentrated hydrochloric acid at 20°-25° C. was added 10.66parts (0.052 mole) of 5N sodium nitrite solution. The color of thesuspension changed from white to very pale cream, and the temperaturerose 3-4' C. A positive nitrite test was maintained for 30 minutes andthe excess nitrite was then destroyed by the addition of sulfamic acid.

A solution of 12.92 parts (0.055 mole) ofN-ethyl-N'-(3-diethylamino)phenyl urea in 100 parts of acetic acid wasadded dropwise over 30 minutes to the suspension of the diazoniumcompound at 20°-25° C. The slurry turned red and the intermediatemonoazo dye precipitated out as the diazonium slurry disappeared. The pHwas raised to 3.5-4.0 by the addition of solid sodium acetate and themixture stirred at room temperature for 16 hours. The solids wereisolated by filtration and washed with water.

The above wet product was suspended in a mixture of 100 parts of acetoneand 100 parts of water. Potassium carbonate (13.8 parts, 0.10 mole) anddiethyl sulfate (15.4 parts, 0.10 mole) were added and the mixturestirred at 25°-30° C. for 16 hours. The alkylated dye precipitated andwas collected by filtration, washed with water and dried to yield 18.71parts (92.0% yield) of red product. Recrystallization from isopropanolprovided an analytically pure sample, a_(max). 117.3 liters g.⁻¹_(cm).⁻¹ at λ_(max). 528 mμ.

The structure of the dye is ##STR29##

EXAMPLE 3

The diazotization of 2-amino-4,5-dicyanoimidazole (0.05 mole) wascarried out essentially as described in Example 2 above.

A solution of 11.33 parts (0.055 mole) of3-(N,N-diethylamino)acetanilide in 50 parts of acetic acid and 50 partsof methanol was added dropwise over 15 minutes at 20°-25° C. to thediazo suspension. The mixture was stirred at 25°-30° C. for 4 hours,filtered and the collected solids washed with water and dried to give15.58 parts (89% yield) of red product.

The above product (3.50 parts, 0.01 mole) was dissolved in 70 parts ofdimethylformamide. Dibasic sodium phosphate (1.42 parts, 0.01 mole) anddimethyl sulfate (4.0 parts, 0.032 mole) were added and the reactionmixture heated at 80° C. for 2 hours. A small amount of cationic dye, asevidenced by the presence of a red baseline spot in the thin-layerchromatogram of the reaction mass, was also formed in addition to thedesired alkylated disperse dye. The reaction mass way cooled to 25°-30°C., filtered to remove the acid-binding agent, and the filtrate drownedin 300 parts of water. The solids were isolated by filtration, washedwith water and dried to give 2.73 parts (75% yield) of red product. Thinlayer chromatography on silica gel coated glass plates usingbenzene-acetonitrile (4:1) as eluent showed only one red spot and noneof the cationic dye originally detected was present in the isolatedproduct. Recrystallization from isopropanol provided an analyticallypure sample, a_(max). 132 liters g..sup. -1 cm.⁻¹ at λ_(max). 523 mμ.

The structure of the dye is ##STR30##

EXAMPLE 4

The intermediate azo compound of Example 3 (7.0 parts, 0.02 mole)##STR31## was dissolved in 120 parts of dimethylformamide. Dibasicsodium phosphate (2.84 parts, 0.02 mole) and allyl chloride (7.6 parts,0.10 mole) were added and the mixture heated at 80° C. for 18 hours. Thereaction mass was cooled to 25°-30° C., filtered, and the filtratedrowned in 300 parts of water. The solids were isolated by filtration,washed with water and dried to give 5.46 parts (70% yield) of redproduct. Column chromatography on silica gel using chloroform as eluentprovided an analytical pure sample, a_(max). 124 liters g.⁻¹ cm.⁻¹ atλ_(max). 540 mμ.

The structure of the dye is ##STR32##

EXAMPLE 5

The intermediate azo compound of Example 3 (3.50 parts, 0.01 mole) wassuspended in 50 parts of acetone and 50 parts of water containing 1.52parts (0.011 mole) of potassium carbonate. Benzyl chloride (6.35 parts,0.050 mole) was added and the reaction stirred at 25°-30° C. for 72hours. Thin layer chromatography showed that considerable unalkylatedstarting material remained. The solids were collected by filtration,washed with water and dried and give 2.3 parts (52% yield) of redproduct. Thin layer chromatography showed only one red spot, andunalkylated dye was retained in the filtrate. The product had ana_(max). of 112 liters g. ⁻¹ cm.⁻¹ at λ_(max). 542 mμ.

The structure of the dye is ##STR33##

EXAMPLE 6

The intermediate azo compound of Example 3 (3.50 parts, 0.01 mole) wasdissolved in 70 parts of dimethylformamide. Dibasic sodium phosphate(1.42 parts, 0.01 mole) and 1,2-butylene oxide (2.16 parts, 0.03 mole)were added and the mixture heated at 60° C. for 48 hours. The reactionmixture was cooled to 25°-30° C. and the solids were collected byfiltration, washed with water and dried. Thin layer chromatographicanalysis of the product revealed only one red spot.

The above alkylated product (0.90 part) was dissolved in 20 parts ofpyridine and 2.2 parts of acetic anhydride were added. The mixture washeated at 80° C. for 4 hours, cooled to 25°-30° C. and the finaldyestuff precipitated by the dropwise addition of 50 parts of water. Thesolids were filtered, washed with water and dried to give 0.80 part ofred product, a_(max). 103 liters g. ⁻¹ cm.⁻¹ at λ_(max). 540 mμ.

The structure of the dye is ##STR34##

EXAMPLE 7 To 160 parts of water and 7.91 parts (0.081 mole) ofconcentrated hydrochloric acid were added 6.65 parts (0.050 mole) of2-amino-4,5-dicyanoimidazole. 10.66 Parts (0.052 mole) of 5N sodiumnitrite solution were added rapidly at 20°-25° C. A positive nitritetest was maintained for 30 minutes and the excess nitrite was thendestroyed by the addition of sulfamic acid.

A solution of 7.15 parts (0.05 mole) of α-naphthylamine in 50 parts ofacetic acid was then added over a period of 30 minutes to the diazosuspension at 20°-25° C. The reaction mass became thick as couplingproceeded; it was diluted with 200 parts of water.

The pH was adjusted to 6.5 with 30% aqueous caustic soda, during whichprocedure the temperature rose to 40°-50° C. The intermediate monoazoamine was isolated by filtration, washed thoroughly with water, anddried to yield 12.2 parts (85% yield) of product.

14.35 Parts (0.050 mole) of the above monoazo amine were slurried to asmooth paste in a mixture of 100 parts of acetic acid, 80 parts of waterand 7.91 parts (0.081 mole) of concentrated hydrochloric acid. 10.66Parts (0.052 mole) of 5N sodium nitrite solution were added over a5-minute period at 25°-30° C. After maintaining an excess of nitrite for30 minutes, the excess was destroyed with sulfamic acid.

A solution of 11.33 parts (0.055 mole) of3-(N,N-diethylamino)acetanilide in 100 parts of acetic acid was thenadded to the diazo solution over a period of 30 minutes at 20°-25° C.;the reaction was allowed to proceed until there was no longer anydiscernible diazonium salt in the reaction mixture. The pH was raised to3.5-4.0 by the addition of solid sodium acetate and the slurry stirredfor 2 hours. The solids were isolated by filtration, washed thoroughlywith water and dried to yield 18.4 parts (73% yield) of blue product,a_(max). 69 liters g.⁻¹ cm.⁻¹ at λ_(max). 555 mμ.

24.5 Parts (0.050 mole) of the above bisazo intermediate were suspendedin a mixture of 100 parts of acetone and 100 parts of water. 13.8 Parts(0.10 mole) of potassium carbonate and 15.4 parts (0.10 mole) diethylsulfate were added and the mixture stirred at 25°-30° C. for 16 hours.The solids were isolated by filtration, washed with water and dried toyield 21.3 parts (80% yield) of blue product, a_(max). 98 liters g. ⁻¹cm.⁻¹ at λ_(max). 638 mμ.

The structure of the dye is ##STR35##

EXAMPLES 8-133

Examples 8-133 were prepared by procedures similar to those described inExamples 1-7.

                                                                                     ##STR36##                                                                      Example         λ .sub.max. a .sub.max. Shade on No. R.sub.1           R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6 W m (mμ) (1. g. .sup.- cm.          .sup.-1) Polyester                                                               8 CH.sub.3 H C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H N     HCOCH.sub.3 -- 0 518 100 Scarlet 9 CH.sub.3 H C.sub.2 H.sub.5 CH.sub.2         CH(OH)CH.sub.2 OC.sub.6 H.sub.5 H CH.sub.3 -- 0 516 106 Scarlet 10             CH.sub.3 H CH.sub.3 CH.sub.3 H NHCOC.sub.6 H.sub.5 -- 0 522 123 Red 11         CH.sub.3 H C.sub. 2 H.sub.4 CO.sub.2 CH.sub.3 C.sub.2 H.sub.4 CO.sub.2         CH.sub.3 H NHCOCH.sub.3 -- 0 518 106 Scarlet 12 CH.sub.3 H C.sub.2             H.sub.5 C.sub.2 H.sub.4 CO.sub.2 CH.sub.3 H NHCOCH.sub.3 -- 0 521 127          Red 13 CH.sub.2 CH(OH)C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5        H NHCOCH.sub.3 -- 0 530 125 Red 14 CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5         CH.sub.2 C.sub.6 H.sub.5 H NHCOCH.sub.3 -- 0 520 124 Red 15 C.sub.2            H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 528 126          Red 16 (CH.sub.2).sub.3 CH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H           NHCOCH.sub.3 -- 0 535 139 Red 17 C.sub.2 H.sub.5 H (CH.sub.2).sub.3            CH.sub.3 (CH.sub.2).sub.3 CH.sub.3 H NHCOCH.sub.3 -- 0 533 142 Red 18          C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.2 C.sub.6                              H.sub.5 H NHCOCH.sub.3 -- 0 527 141 Red 19 C.sub.2 H.sub.5 H C.sub.2          H.sub.5 CH.sub.2 CH(OH)C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 530 120 Red         20 CH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 -- 0 515 147          Scarlet 21 CH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 OH H CH.sub.3 -- 0       518 128 Scarlet 22 CH.sub.3 H C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH H          NHCOCH.sub.3 -- 0 519 123 Scarlet 23 CH.sub.2 CH.sub.2                          CH.sub.3 OCH.sub.3 C.sub.2 H.sub.4 CN H H NHCOCH.sub.3 -- 0 545 107 Red       24 CH.sub.2 CH.sub.2 CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5        H NHCOCH.sub.3 -- 0 567 118 Bordeaux 25 CH.sub.2 CH.sub.2 CH.sub.3             OCH.sub.3 C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOCH.sub.3        -- 0 533  82 Red 26 CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2 H.sub.5 C.sub.2       H.sub.4 CN H CH.sub.3 -- 0 502 104 Orange 27 C.sub. 2 H.sub.5CH.sub.2          CH(OC.sub.2 H.sub.4 CN)CH.sub.2 C.sub.2 H.sub.5 H CH.sub.3 -- 0 520 117        Scarlet 28CH.sub.2 CH.sub.2 CH.sub.3HC.sub.2 H.sub.4 CNC.sub.2 H.sub.4         OHHCH.sub.3 --O515 106Scarlet 29CH.sub.2 CH.sub.2 CH.sub.3H C.sub.2            H.sub.4 CN C.sub.2 H.sub.4 OCOCH.sub.3 H CH.sub.3 -- 0 492  83 Orange 30       CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2 H.sub.4 CN H H NHCOCH.sub.3 -- 0          508 106 Scarlet 31 CH.sub.2 CH.sub.2 CH.sub.3 H CH(CH.sub.3).sub.2             CH.sub.2 CH(OCOCH.sub.3)C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 528 101            Scarlet 32 CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2 H.sub.4 CN CH.sub.2            CH(OCOCH.sub.3)C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 512  62 Scarlet 33          CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OH H           NHCOCH.sub.3 -- 0 518 113 Red 34 CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2          H.sub.4 CN CH.sub.2 CH(OH)C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 517 112          Scarlet 35 CH.sub.3 H CH.sub.3 CH.sub.3 H NHCOC(CH.sub.3).sub.3 -- 0 515       123 Scarlet 36 C.sub.2 H.sub.5 H C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2           H.sub.4 OCOCH.sub.3 H NHSO.sub.2 CH.sub.3 -- 0 535  80 Red 37 C.sub.2          H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCO.sub.2 CH.sub.3 -- 0 517       142 Scarlet 38 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H             NHCOC.sub.3 H.sub.7 -- 0 522 138 Red 39 C.sub.2 H.sub.5 H C.sub.2              H.sub.5 C.sub.2 H.sub.5 H NHCOC.sub.7 H.sub.15 -- 0 520 113 Red 40             C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCONHC.sub.4              H.sub.9 -- 0 525 119 Cerise 41 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2       H.sub.5 H NHCO.sub.2 C.sub.6 H.sub.13 -- 0 518 116 Scarlet 42 C.sub.2          H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.2 H.sub.4         OC.sub.2 H.sub.5 -- 0 518 132 Scarlet 43 C.sub.2 H.sub.5 H C.sub.2             H.sub.5 C.sub.2 H.sub.5 H NHCO.sub.2 C.sub.2 H.sub.5 -- 0 519 131              Scarlet 44 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2                            H.sub.5 H NHCOCH.sub.2 OC.sub.2 H.sub.5 -- 0 520 106 Red 45 C.sub.2           H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 Cl -- 0 522 126       Red 46 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHSO.sub.2          CH.sub.3 -- 0 535 115 Red 47 C.sub.2 H.sub.5 H C.sub.2 H.sub.4                  OCOC.sub.2 H.sub.5 C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5 H NHCOC.sub.2           H.sub.5 -- 0 514  87 Scarlet 48 C.sub.2 H.sub.5 H C.sub.2 H.sub.4              CCOC.sub.3 H.sub.7 C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 H NHCOC.sub.3            H.sub.7 -- 0 514  74 Scarlet 49 C.sub.2 H.sub.5 H C.sub.2 H.sub.5              CH.sub.2 C.sub.6 H.sub.5 H CH.sub.3 -- 0 509 113 Scarlet 50 CH.sub.2           C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 -- 0 526          134 Red 51 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.2 CH(OH)C.sub.2            H.sub.5 H CH.sub.3 -- 0 518 134 Scarlet 52 C.sub.2 H.sub.5 H C.sub.2           H.sub.5 C.sub.2 H.sub.5 H CH(OH)CH.sub.3 -- 0 518 130 Red 53 C.sub.2           H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 CO.sub.2 CH.sub.3 H CH.sub.3         -- 0 508 117 Orange 54 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5       H OH -- 0 514 137 Orange 55 CH.sub.3 H C.sub.2 H.sub.4 CO.sub.2 C.sub.2        H.sub.4 OC.sub.2 H.sub.5 H H NHCOCH.sub.3 -- 0 502  93 Orange 56               CH.sub.3 CH.sub.2 CH(OH)CH.sub.2 H CHCHCHCH -- 0 571 143 Red-Violet 57         C.sub.2 H.sub.5 CH.sub.2                                                        CH(OH)CH.sub.2 H CHCHCHCH -- 0 572 140 Red-Violet            58               CH.sub.2 CH.sub.2                                                               CH.sub.3 H                                                                    ##STR37##                                                                       H CHCHCHCH -- 0 547  84 Bordeaux 59 CH.sub.3 H C.sub.2 H.sub.4                 CONH.sub.2 H CHCHCHCH -- 0 542  97 Bordeaux 60 CH.sub.3 H C.sub.2             H.sub.4 CONHCH.sub.3 H CHCHCHCH -- 0 541  89 Bordeaux 61 C.sub.2 H.sub.5       H C.sub.2 H.sub.5 H CHCHCHCH -- 0 550 129 Bordeaux 62 C.sub.2 H.sub.5 H        C.sub.2 H.sub.5 C.sub.2 H.sub.5 CHCHCHCH -- 0 542 117 Bordeaux 63              CH.sub.2 CH.sub.2 CH.sub.3 H C.sub.2 H.sub.4 CH H CHCHCHCH -- 0 540  91        Bordeaux 64 C.sub.2 H.sub.5 CH.sub.2 CH(OCOC.sub.5 H.sub.11)CH.sub.2 H   C     CHHCHCH -- 0 558 101 Reddish             65 C.sub.2 H.sub.5 H C.sub.2          H.sub.5 C.sub.2                                                                 H.sub.5 H NHCOCH.sub.3                                                        ##STR38##                                                                       1 610 107 Blue 66 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H         CH.sub.3                                                                        ##STR39##                                                                      1 630  93 Blue 67 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H         CH.sub.3                                                                        ##STR40##                                                                      1 627 106 Blue            68 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2        H.sub.5 CHCHCHCH                                                                ##STR41##                                                                      1 520  53 Red-Violet 69 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.2            CH(OH)CH.sub.2 OC.sub.6 H.sub.5 H CH.sub.3 -- 0 515 100 Scarlet 70             C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.2 CH(OH)C.sub.6 H.sub.5 H H --        0 512  87 Scarlet 71 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.2                 CH(OH)CH.sub.2 Cl H CH.sub.3 -- 0509 106 Scarlet 72 C.sub.2 H.sub.5 H         C.sub.2 H.sub.5 C.sub.2 H.sub.5 H Cl -- 0 511 129 Scarlet 73 CH.sub.3 H        C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOC.sub.3 H.sub.7 -- 0 525 133 Red         74 CH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.5 -- 0       528 123 Red 75 C.sub.2 H.sub.5 H C.sub.2 H.sub.5C.sub.2 H.sub.5H               NHCOC.sub.2 H.sub.5 -- 0 525 132 Red 76 C.sub.2 H.sub.5 H CH.sub.3             CH.sub.3 H NHCOCH.sub.3 -- 0 520 135 Red 77 CH.sub.3 H CH.sub.3 CH.sub.3       H NHCOCH.sub.3 -- 0 519 135 Red 78 C.sub.2 H.sub.5 H C.sub.2 H.sub.5           C.sub.2 H.sub.5 H NHCOC(CH.sub.3).sub.3 -- :500 127 Red 79 CH.sub.2            C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCO.sub.2 CH.sub.3        -- 0 520 136 Red 80 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2         H.sub.5 H NHCOC.sub.3 H.sub.7 -- 0 528 122 Red 81 CH.sub.2 CHCH.sub.2 H        C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCO.sub.2 CH.sub.3 -- 0 515 122 Red         82 CH.sub.2 CHCH.sub.2 H C.sub.2 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 H            CH.sub.3 -- 0 510 104 Scarlet 83 C.sub.2 H.sub.5 H C.sub.2 H.sub.5             CH.sub.2 CH(OH)CH.sub.2 CN H CH.sub.3 -- 0 510 107 Scarlet 84 C.sub.2          H.sub.5 H C.sub.2 H.sub.5 CH.sub.2 C.sub.6 H.sub.4(3')NO.sub.2 H               CH.sub.3 -- 0 503 107 Scarlet 85 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H           C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 -- 0 515 111 Red 86 CH.sub.2        CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H          CH.sub.3 -- 0 515 118 Red 87 CH.sub.2 CHCHC.sub.6 H.sub.5 H C.sub.2            H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 -- 0 508 105 Scarlet 88 CH.sub.2            C.sub.6 H.sub.4(3')NO.sub.2 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3       -- 0 525  98 Red 89 CH.sub.2 C.sub.6 H.sub.4(4')Cl H C.sub.2 H.sub.5           C.sub.2 H.sub.5 H CH.sub.3 -- 0 520 119 Red 90 C.sub. 2 H.sub.5 H               ##STR42##                                                                      H CH.sub.3 -- 0   Scarlet 91 C.sub.2 H.sub.5 OCH.sub.3 C.sub.2 H.sub.4        CN H H NHCOCH.sub.3 -- 0   Red 92 C.sub.2 H.sub.5 H C.sub.2 H.sub.5            CH.sub.2 C.sub.6 H.sub.4(4')Cl H CH.sub.3 -- 0   Red 93 CH.sub.2 C.sub.6       H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOC.sub.2 H.sub.5 -- 0           Cerise 94 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2                             H.sub.5 H NHCOCH.sub.2 OH -- 0   Red 95 C.sub.2 H.sub.5 H C.sub.2             H.sub.4 CN CH.sub.2 CH(OH)CH.sub.2 OC.sub.6 H.sub.6 H NHCOCH.sub.3 -- 0         Scarlet 96 C.sub.2 H.sub.5 H CH.sub.2 CH(OH)CH.sub.2 OC.sub.6 H.sub.5         CH.sub.2 CH(OH)CH.sub.2 OC.sub.6 H.sub.5 H NHCOCH.sub.3 -- 0   Red 97          CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 OH H             CH.sub.3 -- 0   Scarlet 98 CH.sub.2 C.sub.6                                     H.sub.5 H                                                                     ##STR43##                                                                       H H CH.sub.3 -- 0   Scarlet 99 CH.sub.2 C.sub.6                                H.sub.5 H                                                                     ##STR44##                                                                       H H NHCOCH.sub.3 -- 0   Red 100 C.sub.2 H.sub.5 H C.sub.2 H.sub.4             OC.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OC.sub.2 H.sub.4 CN H CH.sub.3 -- 0         Orange 101 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2                           H.sub.5 H NHCOCH.sub.2 OC.sub.2 H.sub.4 CN -- 0   Orange 102 C.sub.2          H.sub.5 H CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2 H NHCOCH.sub.3 -- 0 Red          103 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 CN H  NHCOCH.sub.3       -- 0 Scarlet 104 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 CN H        NHCOC.sub.2 H.sub.5 -- 0 Scarlet 105 C.sub.2 H.sub.5 H C.sub.2 H.sub.5         C.sub.2 H.sub.4 CN H NHCOC.sub.3 H.sub.7 -n -- 0 Scarlet 106 C.sub.2           H.sub.5 H C.sub.2 H.sub.4 OCONHC.sub.4 H.sub.9 -n C.sub.2 H.sub.4              OCONHC.sub.4 H.sub.9 -N H NHCOCH.sub.3 -- 0 Red 107 C.sub.2 H.sub.5 H          C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n H NHCOCH.sub.3        -- 0 Scarlet 108 C.sub.2 H.sub.5 H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4          OCONHC.sub.4 H.sub.9 -n H NHCOCH.sub.3 -- 0 Scarlet 109 CH.sub.2 C.sub.6       H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 CN H NHCOC.sub.2 H.sub.5 -- 0        Scarlet 110 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4         CN H NHCOC.sub.3 H.sub.7 -n -- 0 Scarlet 111 CH.sub. 2 C.sub.6 H.sub.5H        CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2 H NHCOCH.sub.3 -- 0 Cerise 112             CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 OCONHC.sub.4        H.sub.9 -n H CH.sub.3 -- 0 Scarlet 113 CH.sub.2 C.sub.6 H.sub.5 H              C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOCH.sub.3 -- 0             Scarlet 114 CH.sub.2 C.sub.6 H.sub.5H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4       OCOC.sub.3 H.sub.7 -n H NHCOCH.sub.3 -- 0 Scarlet 115 CH.sub.2 C.sub.6         H.sub.5 H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 OCONHC.sub.4 H.sub.9 -n H         NHCOCH.sub.3 -- 0 Scarlet 116 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5       C.sub.2 H.sub.5 H NHCOCH.sub.2 OH -- 0 Cerise 117 CH.sub.2 C.sub.6             H.sub.5 H CH.sub.3 CH.sub.3 H NHCOC.sub.2 H.sub.5 -- 0 Red 118 CH.sub.2        C.sub.6 H.sub.5 H CH.sub.3 CH.sub.3 H NHCOC.sub.3 H.sub.7 -n -- 0 Red          119 C.sub.2 H.sub.5 H C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 CO.sub.2              C.sub.2 H.sub.5 H NHCOCH.sub.3 -- 0 Orange 120 C.sub.2 H.sub.5 H C.sub.2       H.sub.4 CN C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n H NHCOCH.sub.3 --       0 Orange 121 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 OC.sub.2        H.sub.4 CN H CH.sub.3 -- 0 Scarlet 122 C.sub.2                                  H.sub.5 H CH(CH.sub.3).sub.2 C.sub.2 H.sub.4 CN H NHCOCH.sub.3 -- 0           Scarlet 123 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 OH H             NHCOC.sub.2 H.sub.5 -- 0 Red 124 C.sub.2 H.sub.5 H C.sub.2 H.sub.5             C.sub.2 H.sub.4 OH H NHCOC.sub.3 H.sub.7 -n -- 0 Red 125 CH.sub.2              C.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.3 H               CH.sub.3 -- 0 Scarlet 126 CH.sub. 2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5          C.sub.2 H.sub.4 NHCONHC.sub.6 H.sub.5 H CH.sub.3 -- 0 Red 127 CH.sub.2         C.sub.6 H.sub.5 H C.sub.2                                                       H.sub.5                                                                       ##STR45##                                                                       H CH.sub.3 -- 0 Scarlet 128 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5        C.sub.2 H.sub.4 NHCOCH.sub.2 OH H CH.sub.3 -- 0 Red 129 CH.sub.2 C.sub.6       H.sub.5HC.sub.2                                                                 H.sub.5                                                                       ##STR46##                                                                       H CH.sub.3 -- 0 Scarlet 130 CH.sub.2 C.sub.6 H.sub.5 H C.sub.2 H.sub.5        C.sub.2 H.sub.4 NHCOC.sub.6 H.sub.5 H CH.sub.3 -- 0 Scarlet 131 CH.sub.2       C.sub.6                                                                         H.sub.5 H                                                                     ##STR47##                                                                       C.sub.2 H.sub.4 CN H CH.sub.3 -- 0 Orange 132 C.sub.2 H.sub.5 H               CH.sub.2 C.sub.6 H.sub.5 H H NHCOCH.sub.3 -- 0 Scarlet 133 CH.sub.2            C.sub.6 H.sub.5 H C.sub.2 H.sub.4 CN H H NHCOC.sub.2 H.sub.5 -- 0              Scarlet                                                                   

EXAMPLES 134-136

A suspension of 2-diazo-4,5-dicyanoimidazole (0.050 mole) was preparedas described in Example 2.

A solution of 7.92 parts (0.055 mole) of 2-naphthol and 2.20 parts(0.055 mole) of sodium hydroxide in 100 parts of water and 50 parts ofdimethylformamide was added dropwise over 30 minutes to the suspensionof the diazonium compound at 20°-25° C. The slurry turned red and theintermediate monoazo dye precipitated out as the diazonium slurrydisappeared. The slurry was stirred at 20°-25° C. for 4 hours whilemaintaining the pH at 9-11 by the addition of 10% sodium hydroxidesolution as required. After coupling was complete, the pH was adjustedto 5.0 with concentrated hydrochloric acid and stirred for 1 more hourat 25°-30° C. The solids were isolated by filtration, washed with waterand dried to give 12.24 parts (85% yield) of red product.

14.40 Parts (0.05 mole) of the above product were suspended in a mixtureof 100 parts of acetone and 100 parts of water. Potassium carbonate(13.8 parts, 0.10 mole) and diethyl sulfate (15.4 parts, 0.10 mole) wereadded and the mixture stirred at 25°-30° C. for 16 hours. The alkylateddye precipitated and was collected by filtration, washed with water anddried to give 12.56 parts (80% yield) of red product. Thin layerchromatography showed the product to consist mainly of the desired redN-alkylated dye together with a small amount of a second red componentpresumably being formed by the alkylation of the hydroxy substituent inthe coupling component. Column chromatography on silica gel usingchloroform as solvent provided the pure dye, a _(max). 87 liters g. ⁻¹cm.⁻¹ at λ_(max). 524 mμ.

The structure of the dye is ##STR48##

In similar fashion, coupling of 2-diazo-4,5-dicyanoimidazole to3-methoxycarbonyl-2-naphthol and 3-t-butylcarbamoyl-2-naphthol, followedby alkylation with diethyl sulfate provided the following two dyes##STR49##

EXAMPLE 135 ##STR50## EXAMPLE 136 EXAMPLE 137

A suspension of 0.05 mole of 2-diazo-4,5-dicyanoimidazole was preparedas described in Example 2.

A solution of 9.1 parts (0.055 mole) of 1-phenyl-3-methyl-5-pyrazolonein 150 parts of dimethylacetamide was added to the diazo suspension over15 minutes at <10° C. 6.6 Parts (0.05 mole) of sodium acetate were addedand the mixture stirred for 4 hours at <10° C. The solids were isolatedby filtration, washed with water and dried to give 19.1 parts (60%yield) of golden yellow needles.

A mixture of 15.9 parts (0.050 mole) of the above product, 100 parts ofacetone, 100 parts of water, 13.8 parts (0.10 mole) of potassiumcarbonate and 12.6 parts (0.10) mole of dimethyl sulfate was stirred at25°-30° C. for 16 hours. The yellow solids were isolated by filtration,washed with water and dried to give a quantitiative yield (16.5 parts)of yellow crystalline product, a_(max). 67 liters g.⁻¹ cm⁻¹ at λ_(max).450 mμ. Thin layer chromatography revealed the presence of a singleyellow component.

The structure of the dye is ##STR51##

EXAMPLE 138

A suspension of (0.05 mole) 2-diazo-4,5-dicyanoimidazole was prepared asdescribed in Example 2.

The above diazo suspension was added dropwise over 15 minutes to asolution of 12.0 parts (0.050 mole) of 1,3-di-n-butyl barbituric acid,2.0 parts (0.050 mole) of sodium hydroxide and 7.48 parts of sodiumcarbonate in 300 parts of water at 0-5° C. The mixture was allowed towarm to 25°-30° C. and stirred for 4 hours. The solids were filtered,washed with water and dried to yield 18.58 parts of yellow product.

3.83 Parts (0.01 mole) of the above product were suspended in 100 partsof acetone. Potassium carbonate (2.76 parts, 0.02 mole) was added andthe reaction mixture stirred for 5 minutes at 25°-30° C. 1-Iodobutane(9.20 parts, 0.050 mole) was added and the reaction mixture heated at60° C. for 16 hours. The acetone was then partially evaporated and theresidue diluted with 100 parts of water whereupon an oily layerseparated. The mixture was extracted with two 200 part portions ofchloroform and the combined chloroform extracts dried over anhydroussodium sulfate. The solvent was removed by distillation and the residuerecrystllized from benzenemethanol to yield 4.3 parts (73.4% yield) ofyellow product, a_(max). 57 liters g..sup. -1 cm.⁻¹ at λ_(max). 395 mμ.

The structure of the dye is ##STR52##

EXAMPLES 139-156

Examples 139--156 were prepared in a fashion similar to Examples 137 and138 from 2-diazo-4,5-dicyanoimidazole and various heterocyclic couplingcomponents.

    __________________________________________________________________________     ##STR53##                                                                    Example                     λ.sub.max.                                                                 a.sub.max.                                                                            Shade on                              No.  R.sub.1                                                                             A                (mμ)                                                                           (l. g..sup.-1 cm..sup.-1)                                                             Polyester                             __________________________________________________________________________    139  CH.sub.3                                                                            1-(4'-chlorophenyl)-3-methyl-                                                                  430 65      Yellow                                           5-aminopyrazole                                                    140  C.sub.2 H.sub.5                                                                     "                430 58      Yellow                                141  C.sub.3 H.sub.7                                                                     "                435 56      Yellow                                142  CH.sub.3                                                                            1-ethyl-3-cyano-4-methyl-6-                                                                    435 92      Yellow                                           hydroxy-pyrid-2-one                                                143  CH.sub.2 C.sub.6 H.sub.5                                                            "                440 108     Yellow                                144  CH.sub.3                                                                            1-n-hexyl-3-cyano-4-methyl-6-                                                                  430 92      Yellow                                           hydroxy-pyrid-2-one                                                145  CH.sub.2 C.sub.6 H.sub.5                                                            "                435 85      Yellow                                146  CH.sub.3                                                                            1-benzyl-3-cyano-4-methyl-6-                                                                   430 97      Yellow                                           hydroxy-pyrid-2-one                                                147  CH.sub.2 C.sub.6 H.sub.5                                                            "                435 83      Orange                                148  C.sub.2 H.sub.5                                                                     1-n-butyl-3-cyano-4-methyl-6-                                                                  430 102     Yellow                                           hydroxy-pyrid-2-one                                                149  (CH.sub.2).sub.3 CH.sub.3                                                           "                430 95      Yellow                                150  CH.sub.3                                                                            1,3-dimethyl barbituric acid                                                                   395 59      Yellow                                151  CH.sub.3                                                                            1,3-dicyclohexyl barbituric                                                                    395 64      Yellow                                           acid                                                               152  CH.sub.3                                                                            1-methyl-3-phenyl barbituric                                                                   395 54      Yellow                                           acid                                                               153  C.sub.3 H.sub.7                                                                     1-phenyl-3-methyl-5-pyrazolone                                                                 450 57      Yellow                                154  CH.sub.2 C.sub.6 H.sub.5                                                            "                450 59      Yellow                                155  C.sub.2 H.sub.5                                                                     4-hydroxycoumarin                                                                              455 78      Yellow                                156  C.sub.2 H.sub.5                                                                     2-methylindole   437 99      Yellow                                __________________________________________________________________________

The following Examples typify the previously discussed aqueous andThermosol dyeing procedures.

EXAMPLE 157 - Aqueous (Pressure) Dyeing Procedure

Five grams of polyester fabric were put in an autoclave containing:

an aqueous dye paste (15% active ingredient) containing the dye ofExample 1 . . . 0.1 gram

a long chain anionic sodium hydrocarbon sulfonate (10% solution) . . .1.0 ml.

a long chain nonionic alcohol-ethylene oxide adduct (10% solution) . . .0.5 ml.

ethylenediaminetetraacetic acid, sodium salt (1% solution) . . . 1.25ml.

butyl benzoate carrier (10% solution) . . . 1.5 ml.

water . . . to 75 ml.

acetic acid . . . to adjust the pH to 5.5

The contents of the autoclave were heated for 1 hour at 265° F. The dyedfabric was then rinsed in water and dried. The polyester fabric was dyeda bright red shade.

EXAMPLE 158 Thermosol Procedure

A pad bath was prepared containing:

an aqueous dye paste (15% active ingredient)

containing the dye of Example 23 . . . 50 grams

purified natural gum thickener . . . 20 grams

water . . . to 1 liter

The pad bath was padded on 65/35 polyester/cotton fabric with a pickupof 50-65%, based on dry fabric weight, followed by drying (infraredpredrying followed by hot air or hot can drying is desirable) to removethe water.

Thermosol processing, in which the polyester component is dyed with thedisperse color, was accomplished by treating the dried pigment-paddedfabric for 90 seconds at 213° C. Unfixed surface dye, whether on thepolyester or cotton was removed by padding the fabric from an aqueousbath containing 50 g./l. sodium hydroxide and 40 g./l. sodiumhydrosulfite at 27°-39° C., followed by steaming for 30 seconds. Thefabric was then rinsed in water at 27° C., scoured for 5 minutes at 93°C. in water containing 1% ether alcohol sulfate detergent, rinsed inwater at 27° C. and dried.

After dyeing and cleaning, the material may then be padded (forpermanent press treatment) with a pickup of 50-65% (owf) with a bathcontaining:

    ______________________________________                                                                   g./l.                                              ______________________________________                                        a dimethyloldihydroxyethyleneurea cross-linking                               agent                        200.0                                            a p-octylphenoxy(C.sub.2 H.sub.4 O).sub.9-10 H wetting agent                                               2.5                                              a dispersed acrylic thermoplastic binding                                     agent                        22.5                                             a nonionic, paraffin-free, polyethylene emulsion                              which serves as a fabric softener                                                                          22.5                                             a nonionic polymer emulsion which imparts luster,                             a silky hand and antistatic properties to                                     the fiber                    30.0                                             a 20% aqueous zinc nitrate curing catalyst                                                                 36.0                                             ______________________________________                                    

The resin-impregnated material is then air dried to remove the watercontent and finally cured at 163° C. for 15 minutes.

The durable-press treated polyester/cotton fabric was dyed an attractivebright bluish-red shade.

what is claimed is:
 1. An azo dye of the generic formula ##STR54##wherein R₁ is C₁₋₄ alkyl, --CH₂ --CH═CH₂, ##STR55## --(CH₂)_(n) R₈, C₁₋₄alkyleneCN, C₂ H₄ OR₇, --CH₂ --CH═CH--R₈, --C₂ H₄ CONH₂, --C₂ H₄CONHC₁₋₄ alkyl, --C₂ H₄ CON(C₁₋₄ alkyl)₂ and --C₂ H₄ CO₂ C₁₋₄ -alkyl;Ais a coupling component selected from: a 5-or 6- membered heterocycleconsisting of 5-aminopyrazole, 5-pyrazolone, barbituric acid,6-hydroxypyrid-2-one, 4-hydroxycoumarin and 1,2-dialkylindole; a 1- or2-naphthol group; and an aromatic amine of the formula ##STR56## W is1,4-naphthylene or ##STR57## R₂ is H, F, Cl, C₁₋₄ alkyl, OC₁₋₄ alyl; R₃is cyclohexyl or C₁₋₄ alkylene-R₉ ; R₂ and R₃ together with the nitrogenatom optionally form a 6-membered ring optionally substituted with --OH,OC₂ H₄ CN or OCOC₁₋₅ alkyl. R₄ is H, ##STR58## R₃ and R₄ togetheroptionally form a 6-membered heterocyclic ring containing the nitrogenatom;R₅ is H; R₆ is H, F, Cl, Br, C₁₋₄ alkyl, OC₁₋₄ alkyl, OH, C₁₋₄hydroxyalkyl, NHCOCH═CH₂, NHCOC₁₋₄ alkyl, NHCOR₈, NHCO₂ C₁₋₄ alkyl,NHCONHC₁₋₄ alkyl, NHSO₂ C₁₋₄ alkyl, NHSO₂ R₈, NHCO₂ R₈, NHCONHR₈,NHCOC₁₋₄ alkylene-R₁₀, NHCOC₁₋₄ alkylene-OC₁₋₄ alkylene-R₁₀, NHCO₂ C₁₋₄alkyleneOC₁₋₄ alkyl; R₅ and R₆ together optionally form--CH═CH--CH═CH--; R₇ is H or C₁₋₄ acyl; R₈ is phenyl or phenyloptionally substituted with 1-2 groups selected from Cl, Br, CN, CF₃,NO₂, C₁₋₄ alkyl, OC₁₋₄ alkyl, N(C₁₋₄ alkyl)₂ and NHCOC₁₋₄ alkyl; R₉ isH, OH, CN, COC₁₋₄ alkyl, OCOCH═CH₂, OCOC₁₋₄ alkylene-R₁₁, OCOR₈, CO₂ R₈,CO₂ C₁₋₄ alkylene-R₁₂, ##STR59## OC₁₋₄ alkylene-R₁₀, CONHC₁₋₄alkylene-R₁₁, SO₂ R₈, OCONHC₁₋₄ alylene-R₁₀, NHCOC₁₋₄ alkylene-R₁₀,NHCONHR₈, NHCOR₈ or R₈ ; R₁₀ is CN, OH, Cl, Br or R₇ ; R₁₁ is H, Cl, Br,OC₁₋₄ alkyl or phenyl; R₁₂ is H, OH, OC₁₋₄ alkyl, OCOC₁₋₄ alkylene-R₁₁or OCOR₈ ; R₁₃ and R₁₄ are independently H, C₁₋₄ alkyl, C₁₋₄ alkoxy orCl; m is 0 or 1; and n is 1 to
 3. 2. An azo dye of claim 1 having theformula ##STR60##
 3. An azo dye of claim 1 having the formula ##STR61##4. An azo dye of claim 1 having the formula ##STR62##
 5. An azo dye ofclaim 1 having the formula ##STR63##
 6. An azo dye of claim 1 having theformula ##STR64##
 7. An azo dye of claim 1 having the formula ##STR65##8. An azo dye of claim 1 having the formula ##STR66##
 9. An azo dye ofclaim 1 having the formula ##STR67##
 10. An azo dye of claim 1 havingthe formula ##STR68##
 11. An azo dye of claim 1 having the formula##STR69##
 12. An azo dye of claim 1 having the formula ##STR70##
 13. Anazo dye of claim 1 having the formula ##STR71##
 14. An azo dye of claim1 having the formula ##STR72##
 15. An azo dye of claim 1 having theformula ##STR73##
 16. An azo dye of claim 1 having the formula ##STR74##17. An azo dye of claim 1 having the formula ##STR75##
 18. An azo dye ofclaim 1 having the formula ##STR76##
 19. An azo dye of claim 1 havingthe formula ##STR77##
 20. An azo dye of claim 1 having the formula##STR78##
 21. An azo dye of claim 1 having the formula ##STR79##
 22. Anazo dye of claim 1 having the formula ##STR80##
 23. An azo dye of claim1 having the formula ##STR81##